The field of the invention is chemical and electrical processes for synthesizing metal from a fused bath and the present process is particularly concerned with electrowinning aluminum from a fused bath of cryolite and aluminum compounds.
The state of the art of the electrowinning process begins with U.S. Pat. No. 400,766 and the state of the art of the aluminum reduction cell useful in the present invention may be understood by reference to U.S. Pat. No. 3,400,061 and 4,093,524, the disclosures of which are incorporated herein by reference. Also incorporated by reference herein are U.S. Pat. Nos. 3,028,324; 3,067,124; 3,471,380; 4,333,813; 4,341,611; 4,466,995; 4,466,996; 4,526,911; 4,544,469; 4,560,448; 4,624,766 and European Patent Application 0 021 850 which show the state of the art of protecting cathodes from erosion while electrowinning aluminum.
U.S. Pat. Nos. 3,028,324, 3,471,380 and 4,560,448 disclose particular solutions of titanium in molten aluminum.
Most aluminum metal is smelted by being electrowon from alumina, Al.sub.2 O.sub.3, dissolved in a molten salt electrolyte which is mostly cryolite, Na.sub.3 AlF.sub.6, by a process little changed from that described by Hall (U.S. Pat. No. 400,766, 1889). The cryolite electrolyte usually also contains several percentage of each of aluminum fluoride, AlF.sub.3, and calcium fluoride, CaF.sub.2. The cryolite electrolyte may also contain several percentage of both magnesium fluoride, MgF.sub.2, and lithium fluoride, LiF. The electrolyte fills most of the bottom part of the cavity of the cell including the vertical gap between the cathode and anodes. The electrowinning smelting process is carried out at temperatures that may be as low as 920.degree. C. and/or as high as 1000.degree. C. The usual operating temperature range is from 950.degree. C. to 975.degree. C. Conventional aluminum smelting cells are well described in THE ENCYCLOPEDIA OF ELECTROCHEMISTRY, Reinhold Publishing Corporation, New York, 1964. These conventional cells are constructed with carbon anodes and in modern cells carbon block cathodes, called in the industry "cathode blocks". The carbon blocks hold a cathode pool, often called the cathode pad in the industry, containing up to 12 tons of molten aluminum metal that serves electrochemically as the actual cathode. The whole structure, including the carbon cathode blocks, steel electrical current conductors, insulation, and steel pot shell is known in the industry as the "cathode." The anode is geometrically above the cathode by virtue of the fact that cryolite is slightly lighter than aluminum. It floats on top of the molten aluminum metal and washes around the carbon anodes. The anodes are chemically attacked in the electrowinning smelting process and must be replaced about every two weeks. Cathodes must last the expected 3 to 10 year life of the cell.
The pool of molten aluminum is called the cathode or metal pad. In conventional aluminum reduction cells, the metal cathode pool ranges in depth from 5 to 30 centimeters to produce enough hydrostatic pressure to force the molten metal pool into electrical contact with the carbon cathode blocks. This is necessary because molten aluminum poorly wets the surface of the carbon cathode substrate. Electrical contacts are made with areas of the carbon surface that are momentarily free of electrically insulating materials. At any given moment there are only relatively small areas of good electrical contact between the aluminum pool and the cathode blocks. The remainder of the interface is insulated by a thin layer of molten cryolite, deposits of undissolved alumina ore, and by aluminum carbide, which is a poor electrical conductor. Aluminum carbide readily forms by chemical reaction between molten aluminum metal and carbon of the cathode blocks wherever the two are in contact. Aluminum carbide is somewhat soluble in cryolite electrolyte. It is dissolved away by a layer of cryolite electrolyte that is normally found between most areas of the metal pool and the carbon cathode despite the hydrostatic pressure exerted by the pool of molten aluminum. Cryolite, not aluminum, prefers to wet carbon and aluminum carbide surfaces. All areas of the cathode block carbon surface are periodically eaten away by the process of reacting with aluminum metal to form aluminum carbide which is dissolved away by a layer of molten cryolite. Cryolite is continuously dragged between the aluminum pool and the carbon cathode by motion of the aluminum pool. Wherever aluminum carbide is dissolved away, the carbon cathode blocks may again come into electrical contact with molten metal and for a brief time conduct electricity away from the metal pool. The carbon surface of the cathode is thus steadily eroded away at rates that are typically 1 to 5 centimeters per year.
The top surface of the molten aluminum metal cathode pool is covered by standing and moving waves. The tops of the metal waves tend to short circuit the aluminum electrowinning process by making electrical short circuit paths between the anodes and the cathode. Such shorting results in losses of 6% to 20% in current efficiency in the smelting industry. Most existing smelters have current efficiencies that range from 78% to 90% out of the possible 98% that can be theoretically obtained. The current efficiency is measured by the total amount of metal actually collected from the cell divided by the amount that could have been collected if one aluminum atom were produced for every three electrons that flow through the cell.
Electrical short Circuiting in aluminum reduction cells with metal cathode pools is reduced by increasing the vertical distance between the anode and the cathode to about 5 centimeters. Cryolite based electrolyte in the gap between the cathode and anodes has an electrical resistivity of about 0.42 ohm-cm and carries a direct electrical current of between 0.7 and 1.5 Amperes/cm.sup.2. The electrical current flowing through the cryolite electrolyte in the gap between the anode and the cathode generates electrical heat, and wastes large amounts of electrical power. Reduction of the vertical gap between the cathodes and anodes to 1 to 2 centimeters can save from 2 to 4 kilo Watt hours per kilogram, of aluminum electrovon. This is up to 25% of the power normally required to smelt aluminum. An additional benefit from a drained cathode cell is an increase in cell current efficiency of from 5% to 20%.
The height of the waves on the aluminum pool has been reduced in some of the more recently constructed smelters by computer aided design of the array of electrical conductors that together generate complex patterns of magnetic vectors in the aluminum pool. These magnetic vectors interact with the electrical current flowing in the aluminum pool to cause high metal velocities in the aluminum pool and to generate waves on its surface. Some waves run from side to side, others from end to end while others rotate around the perimeter of the pot. It is most difficult and expensive to reduce the intensities of the various components of the magnetic field in existing smelters to reduce metal motion.
One possible way to prevent the molten aluminum from forming waves is to remove the metal pool from the cathode surface and to smelt aluminum on a raised solid cathode surface. An example of this design of aluminum smelting cell is illustrated by Lewis et al (U.S. Pat. No. 3,400,061). The raised cathode surface must be covered by a coating that is wetted by the molten aluminum. The coating must not be significantly attacked by either the molten cryolite or molten aluminum during operation of the cell. The coating must last from three to five years to give the cell an economically long life.
The desire to reduce the electrical power consumption in the smelting of aluminum has resulted in many conceptual designs for aluminum reduction cells and the construction of a few prototype production cells having solid cathode surfaces drained of aluminum metal. For such a cell to smelt alumina efficiently, aluminum metal must easily wet raised solid cathode surfaces so that the electrowon aluminum metal sticks to the cathode surface and drains off into collection wells away from the areas of electrolysis without being carried off into the cryolite electrolyte as tiny droplets.
Titanium diboride has been identified as a material ideally suited to form the solid cathode surface, Ransley (U.S. Pat. No. 3,028,324, 1962). Whenever titanium diboride is mentioned in this application, it must be understood that the borides of Groups IV-B, V-B and VI-B of the periodic table which include the elements; titanium, zirconium, hafnium, chromium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten and mixtures thereof may be substituted for titanium diboride. Titanium diboride and similar diborides are wetted by aluminum metal, are excellent electrical and thermal conductors and are sparingly soluble in both molten aluminum metal and cryolite based electrolytes.
Some prior United States Patents have attempted to provide this aluminum wetted surface by covering the structural carbon blocks of the cathode with tiles made from titanium and zirconium diborides; Lewis et al (U.S. Pat. No. 3,400,061), Payne (U.S. Pat. No. 4,093,524) and Kaplan (U.S. Pat. No. 4,333,813 and U.S. Pat. No. 4,341,611). Many attempts have been made to coat carbon cathode surfaces of drained cathode aluminum reduction cells with smeared coatings composed of titanium diboride mixed with carbon cement; Boxall et al (U.S. Pat. No. 4,544,469; 4,466,692; 4,466,995; 4,466,996; 4,526,911; 4,544,469 and 4,624,766). Attempts have also been made to form titanium diboride coatings on the surface of the carbon cathode substrate by electroplating prior to producing aluminum metal; Biddulph et al (European Patent Application 0 021 850).
Cathode coatings and structures made according to the various arts found in all previous patents have not yet been successful in providing an aluminum wetted cathode surface that is resistant to both molten aluminum metal and cryolite electrolyte. The aluminum wetted structures produced by each art suffers from at least one of the following failure mechanisms: the coating material is attacked by aluminum metal or cryolite electrolyte; preformed structural shapes are easily cracked and broken by rough handling or by stresses caused by uneven thermal expansion during cell start-up; a difference in the coefficient of thermal expansion between the coating and carbon cathode substrate combined with attaching the coating material at room temperature, with a glue that becomes brittle at a temperature well below the cell operating temperature, causes shear stresses that results in disbondment of the tiles; or the glue is chemically attacked and dissolved by cryolite electrolyte and/or aluminum metal and sodium.
Most patented cathode coating systems for aluminum smelting are based on preformed structures containing titanium diboride which are glued or screwed to the cathode blocks and to the rammed or glued joints between the blocks. Preformed structures may be pure titanium diboride or mixtures of titanium diboride and bonding materials such as carbon and aluminum nitride. Refractory materials structures containing titanium diboride are expensive to fabricate and install in the cell. The glues used are usually various formulations of carbon cement that are bonded together by amorphous carbon. Large shear stresses may develop between titanium diboride preformed structures and the carbon cathode block because both semi-graphitic and graphitic forms of carbon cathode blocks have a lower coefficient of thermal expansion than has titanium diboride. Shear stresses that develop while the cell is heating up to its normal 970.degree. C. operating temperature can cause the glue joint to crack and titanium diboride structures to disbond from the cathode blocks, even before the cell starts to operate. Breakage of titanium diboride structures may occur because of stresses that result from differential thermal expansion during cell heat up. Cells thus constructed can be heated only by slow and careful procedures that properly cure and bake carbon cement and prevent these preformed structures that contain titanium diboride from being mechanically damaged by cracking or spalling.
Special care is required to prevent air burn damage to carbon cement and titanium diboride during the cell heat up step. Typical means of heating cells for start up are to use oil or gas burners to preheat the cathode surface over a period of 8 to 24 hours to a temperature of about 800.degree. C., while the cathode surface is protected by inert or chemically reducing materials that exclude air. When the cell reaches a temperature of about 800.degree. C., molten cryolite is usually poured into the cell and the process of electrowinning aluminum started. Electrical resistance heating associated with electrowinning aluminum is used to further heat the cell to the equilibrium operating balance between electrical heat generated, process heat used and thermal losses.
Any carbon cement glue joint holding structures containing titanium diboride to the carbon cathode substrate that survives cell start up is usually rapidly attacked during cell operation by cryolite, sodium and aluminum, just as the carbon cathode blocks of a conventional aluminum smelting cell are attacked. Aluminum metal tries to wet the titanium diboride side of the glue joint, while cryolite tries to wet the carbon side of the glue joint and dissolve the aluminum carbide formed from the carbon cement.
Carbon cathode blocks Which form the cathode substrate normally undergo from 0.2% to 2% expansion in volume during the first 60 days of cell operation as electroreduced sodium and lithium metals intercalate with the carbon. Any attached structure or cathode coating containing titanium diboride must either swell at the same rate as the carbon blocks or else be able to withstand the stresses caused by cathode block expansion.
Structural shapes containing titanium diboride and carbon that are sintered at temperatures above about 1500.degree. C. are too hard and brittle to be successfully glued to cathode blocks. They either disbond from the cathode blocks while the glue bakes or are too brittle to withstand the incurred stresses which develop during cell start up and normal operation.
Another approach to making an aluminum wetted cathode surface is to mix either coarse chunks or finely divided titanium diboride with carbon cement containing non-graphitic carbon or pitch to form composite materials containing carbon and titanium diboride. These refractory materials having a carbon matrix which binds together dispersed titanium diboride particles are hereby designated carbon-titanium diboride materials. The process and materials for manufacturing structures and coatings of composite materials containing carbon and titanium diboride may be found in U.S. Pat. No. 4,582,555 to Buchta and U.S. Pat. Nos. 4,544,469; 4,466,692; 4,466,995; 4,466,996; 4,526,911; 4,544,469 and 4,624,766 to Boxall et al. If these materials contain over about 20% by volume titanium diboride, they may be wetted on a macroscopic scale by aluminum metal that bridges over the carbon and aluminum carbide between particles of aluminum wetted titanium diboride. Any carbon and aluminum carbide at the surface of the carbon-titanium diboride materials surface is wetted by cryolite. Except for being slowly dissolved by aluminum metal, titanium diboride is essentially chemically inert.
Titanium diboride powder mixed with carbon cement may be smeared onto the cathode block surface in a layer up to about 4 centimeters thick when building the cell cathode. This material may be cured and then baked into a carbon-titanium diboride material as the cell is heated during start-up. Alternatively titanium diboride powder, mixed with carbon cement may be formed into molds and baked into carbon-titanium diboride material structural shapes at temperatures below 1500.degree. C. and then glued to the carbon cathode substrate. Preformed structures containing titanium diboride and carbon which are sintered above 1500.degree. C. are difficult to glue to the cathode blocks. Carbon-titanium diboride materials are generally softer but tougher than carbon-titanium diboride preformed structures sintered above 1500.degree. C.. Carbon-titanium diboride materials that are not heated to over 1200.degree. C. generally adhere to the cathode blocks during cell start up. Carbon-titanium diboride materials structures and coatings however tend to fail rapidly during cell use because cryolite, sodium, and lithium readily penetrate this type of material and react with the non-graphitic carbon matrix to form aluminum carbide. Amorphous carbon contained in carbon cements react more readily with intercalated sodium and lithium and cryolite to form aluminum carbide than does more graphitic forms of carbon.
If aluminum is smelted directly on a carbon-titanium diboride material surface, aluminum carbide forms first on the top surface and along cracks. Considerable mechanical expansion occurs during the formation of aluminum carbide since this material occupies about four times the volume of the carbon required to form it. As aluminum carbide forms along cracks and is dissolved by the cryolite, the coating rapidly disintegrates. Carbon-titanium diboride materials have little resistance to erosion by molten cryolite based electrolytes and are also rapidly oxidized by carbon dioxide bubbles that may be periodically swept against its surface. Carbon-titanium diboride materials may crack and spall due to freeze-thaw damage if cold anodes are placed too close to the cathode and the cryolite freezes onto the cathode surface. Both carbon dioxide attack and freeze-thaw damage is more likely when an anode is inadvertently set lower into the cathode cavity than is intended. If used as a cathode surface in a drained cathode cell, carbon-titanium diboride material layers are typically lost at a rate of about a centimeter per month.
No carbon-titanium diboride materials smeared surface layer, or preformed carbon-titanium diboride materials structure which has been glued onto the cathode blocks, can be mechanically repaired or replaced without shutting the cell down. For an aluminum wetted cathode surface to endure, it must be able to withstand mechanical abuse that is normal to cell operation, including being poked by steel bars and other tools used to work the cell and make measurements, anodes dropping on it, alumina ore deposits that may from time to time fall onto and even freeze to it, cryolite electrolyte freezing, occasional burning by carbon dioxide bubbles, electric arcing caused by short circuits to the anode as well as erosion by strong turbulence in the cryolite electrolyte. A drained cathode aluminum reduction cell does not operate economically and overheats if it looses more than about 15% of its aluminum wetted cathode surface area.